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Fundamental understanding of mechanochemical reactivity is important for designing new mechanophores. Besides the core structure of mechanophores, substituents on a mechanophore can affect its mechanochemical reactivity through electronic stabilization of the intermediate or effectiveness of force transduction from the polymer backbone to the mechanophore. The latter factor represents a unique mechanical effect in considering polymer mechanochemistry. Here, we show that regioisomeric linkage that is not directly adjacent to the first cleaving bond in cyclobutane can still significantly affect the mechanochemical reactivity of the mechanophore. We synthesized three non‐scissile 1,2‐diphenyl cyclobutanes, varying their linkage to the polymer backbone via theo,m, orp‐position of the diphenyl substituents. Even though the regioisomers share the same substituted cyclobutane core structure and similar electronic stabilization of the diradical intermediate from cleaving the first C−C bond, thepisomer exhibited significantly higher mechanochemical reactivity than theoandmisomers. The observed difference in reactivity can be rationalized as the much more effective force transduction to the scissile bond through thep‐position than the other two substitution positions. These findings point to the importance of considering force‐bearing linkages that are more distant from the bond to be cleaved when incorporating mechanophores into polymer backbones.
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Mechanochemistry of cyclobutanes
Abstract The field of polymer mechanochemistry has been revolutionized by implementing force-responsive functional groups—mechanophores. The rational design of mechanophores enables the controlled use of force to achieve constructive molecular reactivity and material responses. While a variety of mechanophores have been developed, this Mini Review focuses on cyclobutane, which has brought valuable insights into molecular reactivity and dynamics as well as innovations in materials. We discuss its reactivity and mechanism, dynamics and stereoselectivity, as well as impacts on material properties.
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- Award ID(s):
- 2204079
- PAR ID:
- 10552023
- Publisher / Repository:
- Springer Nature
- Date Published:
- Journal Name:
- Science China Chemistry
- ISSN:
- 1674-7291
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1007/s11426-024-2344-0
